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At least 613 records · Page 34

Prolonging All-Optical Molecular Electron Spin Coherence in the Tissue Transparency Window

Coherent electron spin states within paramagnetic molecules hold significant potential for microscopic quantum sensing. However, all-optical coherence measurements amenable to high spatial and temporal resolution under ambient conditions remain a significant challenge. Here we conduct room-temperature, picosecond time-resolved Faraday ellipticity/rotation (TRFE/R) measurements of the electron spin decoherence time T 2 * in [IrBr 6 ] 2- . Decoherence is strongly sensitive to solution phase viscosity, pointing to molecular tumbling as an important decoherence mechanism. Accordingly, immobilization of [IrBr 6 ] 2- molecules in thin polymer films results in an order-of-magnitude increase in coherence lifetime and significantly greater magnetic field sensitivity. Here, by tuning energies of ligand-to-metal charge transfer (LMCT) states, TRFE/R enables spin initialization and readout in the tissue transparency window, paving the way toward all-optical, ultrafast molecular electron spin coherence imaging in biological systems.

Electron paramagnetic resonance spectroscopy↗

Breaking the Window of Detection: Using Multi-Scale Solute Tracer Studies to Assess Mass Recovery at the Detection Limit

Stream solute tracers are commonly injected to assess transport and transformation in study reaches, but results are biased toward the shortest and fastest storage locations. While this bias has been understood for decades, the impact of an experimental constraint on our understanding has yet to be considered. Here, we ask how different our understanding of reach- and segment-scale transport would be if our empirical limits were extended. We demonstrate a novel approach to manipulate experimental conditions and observe mass that is stored at timescales beyond the traditional reach-scale window of detection. We are able to explain the fate of an average of 26% of solute tracer mass that would have been considered as “lost” in a traditional study design across our 14 replicates, extending our detection limits to characterize flowpaths that would have been previously unmeasured. We demonstrate how this formerly lost mass leads to predicting lower magnitudes of gross gains and losses in individual reaches, and ultimately show that the network turnover we infer from solute tracers represents an upper limit on actual, expected behavior. Finally, we review the evolution of tracer studies and their interpretation including this approach and provide a proposed future direction to extend empirical studies to not-before-seen timescales.

54 ENVIRONMENTAL SCIENCES↗

Perovskite ink with wide processing window for scalable high-efficiency solar cells

Perovskite solar cells have made tremendous progress using laboratory-scale spin-coating methods in the past few years owing to advances in controls of perovskite film deposition. However, devices made via scalable methods are still lagging behind state-of-the-art spin-coated devices because of the complicated nature of perovskite crystallization from a precursor state. Here we demonstrate a chlorine-containing methylammonium lead iodide precursor formulation along with solvent tuning to enable a wide precursor-processing window (up to ~8 min) and a rapid grain growth rate (as short as ~1 min). Coupled with antisolvent extraction, this precursor ink delivers high-quality perovskite films with large-scale uniformity. The ink can be used by both spin-coating and blade-coating methods with indistinguishable film morphology and device performance. Using a blade-coated absorber, devices with 0.12-cm 2 and 1.2-cm 2 areas yield average efficiencies of 18.55% and 17.33%, respectively. As a result, we further demonstrate a 12.6-cm 2 four-cell module (88% geometric fill factor) with 13.3% stabilized active-area efficiency output.

14 SOLAR ENERGY↗

Disposable ultrasound-sensing chronic cranial window by soft nanoimprinting lithography

Chronic cranial window (CCW) is an essential tool in enabling longitudinal imaging and manipulation of various brain activities in live animals. However, an active CCW capable of sensing the concealed in vivo environment while simultaneously providing longitudinal optical access to the brain is not currently available. Here we report a disposable ultrasound-sensing CCW (usCCW) featuring an integrated transparent nanophotonic ultrasonic detector fabricated using soft nanoimprint lithography process. We optimize the sensor design and the associated fabrication process to significantly improve detection sensitivity and reliability, which are critical for the intend longitudinal in vivo investigations. Surgically implanting the usCCW on the skull creates a self-contained environment, maintaining optical access while eliminating the need for external ultrasound coupling medium for photoacoustic imaging. Using this usCCW, we demonstrate photoacoustic microscopy of cortical vascular network in live mice over 28 days. Finally, this work establishes the foundation for integrating photoacoustic imaging with modern brain research.

47 OTHER INSTRUMENTATION↗

Hot droughts in the Amazon provide a window to a future hypertropical climate

Tropical forests represent the warmest and wettest of Earth’s biomes, but with continued anthropogenic warming, they will be pushed to climate states with no current analogue. Droughts in the tropics are already becoming more intense as they occur at successively higher temperatures. Here, in this study, we synthesize multiple datasets to assess the effects of hot droughts on a central Amazon forest. First, a more than 30-year record of annually resolved forest demographic data from a selective logging experiment showed higher tree mortality during intense droughts, particularly among fast-growing pioneer species with low wood density. Second, analysis of ecophysiological field measurements from the 2015 and 2023 El Niño droughts identified a soil moisture threshold beyond which transpiration rates rapidly declined. As rainless days beyond this threshold continued, drought conditions intensified, increasing the potential for tree mortality from hydraulic failure and carbon starvation. Third, analyses from the Coupled Model Intercomparison Project Phase 6 demonstrated that under high-emission scenarios, a large area of tropical forest will shift to a hotter ‘hypertropical’ climate by 2100. Last, under a hypertropical climate, temperature and moisture conditions during typical dry season months will more frequently exceed identified drought mortality thresholds, elevating the risk of forest dieback. Present-day hot droughts are harbingers of this emerging climate, offering a window for studying tropical forests under expected extreme future conditions.

drought↗

Light self-focusing in the atmosphere: Thin window model

Ultra-high power (exceeding the self-focusing threshold by more than three orders of magnitude) light beams from ground-based laser systems may find applications in space-debris cleaning. The propagation of such powerful laser beams through the atmosphere reveals many novel interesting features compared to traditional light self-focusing. It is demonstrated here that for the relevant laser parameters, when the thickness of the atmosphere is much shorter than the focusing length (that is, of the orbit scale), the beam transit through the atmosphere in lowest order produces phase distortion only. This means that by using adaptive optics it may be possible to eliminate the impact of self-focusing in the atmosphere on the laser beam. Furthermore, the area of applicability of the proposed “thin window” model is broader than the specific physical problem considered here. For instance, it might find applications in femtosecond laser material processing.

42 ENGINEERING↗

Pushing the limits of the electrochemical window with pulse radiolysis in chloroform

Pulse radiolysis (PR) enables the full redox window of a solvent to be accessed, as it does not require electrodes or electrolyte which limit the potentials accessible in voltammetry measurements. PR in chloroform has the additional possibility to enable reaching highly positive potentials because of its large ionization potential (IP). We report PR experiments demonstrated the formation of the (deuterated) chloroform radical cation CDCl 3 + ˙, identifying it as the source of the broad absorption in the visible part of the spectrum. Results indicated that solutes with a redox potential up to +3.7 V vs. Fc/Fc + can be oxidized by CDCl 3 + ˙, which is far beyond what is possible with electrochemical techniques. Oxidation is not efficient because of rapid geminate recombination with chloride counterions, but also due to rapid decomposition of CDCl 3 + ˙ which limits the yield of otherwise longer-lived free ions. The rapid, 6 ± 3 ns, decomposition, confirmed by two independent experiments, means that a solute must be present at a concentration >100 mM to capture >90% of the free holes formed. Addition of ethene removes the broad, overlapping absorptions from ubiquitous (chlorine atom, solute) complexes created by PR in halogenated solvents enabling clear observation of solute cations. The results also unravel the complex radiation chemistry of chloroform including the large reported value G (–CHCl 3 ) = 12 molecules/100 eV for the decomposition of chloroform molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rarefaction windows in a high-power impulse magnetron sputtering plasma

The velocity distribution function of the sputtered particles in the direction parallel to the planar magnetron cathode is studied by spatially- and time-resolved laser-induced fluorescence spectroscopy in a short-duration (20 μs) high-power impulse magnetron sputtering discharge. The experimental evidence for the neutral and ionized sputtered particles to have a constant (saturated) velocity at the end of the plasma on-time is demonstrated. The velocity component parallel to the target surface reaches the values of about 5 km/s for Ti atoms and ions, which is higher that the values typically measured in the direct current sputtering discharges before. The results point out on the presence of a strong gas rarefaction significantly reducing the sputtered particles energy dissipation during a certain time interval at the end of the plasma pulse, referred to as “rarefaction window” in this work. The obtained results agree with and essentially clarify the dynamics of HiPIMS discharge studied during the plasma off-time previously in the work: N. Britun, Appl. Phys. Lett. 99, 131504 (2011)

36 MATERIALS SCIENCE↗

Numerical study of the effect of normalised window size, sampling frequency, and noise level on short time Fourier transform analysis

Photonic Doppler velocimetry, also known as heterodyne velocimetry, is a widely used optical technique that requires the analysis of frequency modulated signals. This paper describes an investigation into the errors of short time Fourier transform analysis. The number of variables requiring investigation was reduced by means of an equivalence principle. Error predictions, as the number of cycles, samples per cycle, noise level, and window type were varied, are presented. The results were found to be in good agreement with analytical models.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

An ultra-thin diamond membrane as a transmission particle detector and vacuum window for external microbeams

Several applications of external microbeam techniques demand a very accurate and controlled dose delivery. To satisfy these requirements when post-sample ion detection is not feasible, we constructed a transmission single-ion detector based on an ultra-thin diamond membrane. The negligible intrinsic noise provides an excellent signal-to-noise ratio and enables a hit-detection efficiency of close to 100%, even for energetic protons, while the small thickness of the membrane limits beam spreading. Moreover, because of the superb mechanical stiffness of diamond, this membrane can simultaneously serve as a vacuum window and allow the extraction of an ion microbeam into the atmosphere.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Stability enhancement of an electrically tunable colloidal photonic crystal using modified electrodes with a large electrochemical potential window

The color tuning behavior and switching stability of an electrically tunable colloidal photonic crystal system were studied with particular focus on the electrochemical aspects. Photonic color tuning of the colloidal arrays composed of monodisperse particles dispersed in water was achieved using external electric field through lattice constant manipulation. However, the number of effective color tuning cycle was limited due to generation of unwanted ions by electrolysis of the water medium during electrical switching. By introducing larger electrochemical potential window electrodes, such as conductive diamond-like carbon or boron-doped diamond, the switching stability was appreciably enhanced through reducing the number of ions generated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where “quantum” coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the “inverted regime” in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory-size three-dimensional x-ray microscope with Wolter type I mirror optics and an electron-impact water window x-ray source

We constructed a laboratory-size three-dimensional water window x-ray microscope that combines wide-field transmission x-ray microscopy with tomographic reconstruction techniques, and observed bio-medical samples to evaluate its applicability to life science research fields. It consists of a condenser and an objective grazing incidence Wolter type I mirror, an electron-impact type oxygen Kα x-ray source, and a back-illuminated CCD for x-ray imaging. A spatial resolution limit of around 1.0 line pairs per micrometer was obtained for two-dimensional transmission images, and 1-μm scale three-dimensional fine structures were resolved.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Digitized detection of gamma-ray signals concentrated in narrow time windows for transient positron annihilation lifetime spectroscopy

A pulsed slow-positron beam generated by an electron linear accelerator was directly used for positron annihilation lifetime spectroscopy without any positron storage devices. A waveform digitizer was introduced to simultaneously capture multiple gamma-ray signals originating from positron annihilation events during a single accelerator pulse. The positron pulse was chopped and bunched with the chopper signals also sent to the waveform digitizer. Time differences between the annihilation gamma-ray and chopper peaks were calculated and accumulated as lifetime spectra in a computer. The developed technique indicated that positron annihilation lifetime spectroscopy can be performed in a 20 μs time window at a pulse repetition rate synchronous with the linear accelerator. Lifetime spectra of a Kapton sheet and a thermally grown SiO{sub 2} layer on Si were successfully measured. Synchronization of positron lifetime measurements with pulsed ion irradiation was demonstrated by this technique.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The effect of periodic wavy profile on suppressing window multipactor under arbitrary electromagnetic mode

The three-dimensional periodic ripple profile with each unit of rotational symmetric surface is proposed to suppress multipactor for arbitrary electromagnetic mode with any polarization. The field distribution and multipactor electron dynamics on the wavy surface are studied to illustrate the multipactor inhibition mechanism. High power microwave experiment was conducted to demonstrate the effect of wavy surface on significantly improving the window power capacity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Graphene/semiconductor silicon modified BiFeO{sub 3}/indium tin oxide ferroelectric photovoltaic device for transparent self-powered windows

We report photovoltaic response of highly transparent graphene/BiFe{sub 0.95}Si{sub 0.05}O{sub 3} (BFSiO)/ITO/glass derived from bottom-up spin coating technique. The device exhibits short-circuit-current (I{sub SC} 0.75 mA) with 1000 fold upsurge and open-circuit-voltage (V{sub OC} ∼ 0.45 V) under standard AM 1.5 illumination through graphene. In combination, I{sub SC} of 0.63 mA and V{sub OC} of 0.35 V for same illumination through ITO, reveals the prospects of harvesting indoor light. Also, crystallographic structure, red shift in band gap, leakage behavior, and ferroelectric characteristics of BFSiO thin films are reported. Reproducible transient response of I{sub SC} and V{sub OC} with quick switching (<100 ms) for 20 consecutive cycles and stability (95%) over test period of 16 weeks signifies high endurance and retentivity, promising for building integrated self-powered windows.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Temporal behavior of unresolved transition array emission in water window soft x-ray spectral region from multiply charged ions

We have characterized the spectral structure and the temporal history of the laser-produced high-Z multi-charged ion plasmas for the efficient water window soft x-ray sources. Strong unresolved transition array emission was observed due to 4d–4f and 4f–5g transitions from Au, Pb, and Bi plasmas in the 280–700 eV photon energy region. The temporal behavior of the emission was essentially similar of that of the laser pulse with a slight delay between different transitions. These results provide feedback for accurate modeling of the atomic processes with the radiative hydrodynamic simulations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗